Herbicidal aminohydrins



United States Patent O 3,464,811 HERBICIDAL AMINOHYDRINS v *Stanley J. Brois, Cranford, N.J., assignor to Esso Research and Engineering Company, a corporation of Delaware I No Drawing. Continuation-impart of application Ser. No. 517,972, Jan. 3, 1966. This application Jan. 24, 1968,

Ser. No. 700,009

Int. Cl. A01n 9/22 US. Cl. 71-88 11 Claims ABSTRACT OF THE DISCLOSURE Agricultural compositions or formulations comprising; (1) aminohydrins of the formula groups and (2) an inert diluent or carrier; and the use of such compositions or formulations as pesticides.

CROSS-REFERENCE TO OTHER APPLICATIONS This application is a continuation-in-part of Stanley J. Brois copending US. patent application Ser. No. 517,972, filed on Jan. 3, 1966 now -U.S. Patent No. 3,401,164.

DESCRIPTION OF THE INVENTION The present invention relates to agricultural compositions or formulations comprising pesticidally active aminohydrins and the use of such compositions as pesticides. In general, the invention is concerned with agricultural compositions or formulations comprisingcompounds of the general formula:

Y-"(iJ-OH R where Y represents DN(CH)..NH

( R R Y NH 0:0 N OH 1 I 3,464,811 Patented Sept. 2, 1969 Non-limiting examples of suitable N(w-aminoalkyl)aziridine derivatives include N(2-aminoethyl)aziridine, N(3- aminopropyDaziridine, and N(4- aminobutyl)az iridine,

etc.

Suitable halo ketones or halo aldehydes are those containing about 2 to 6 carbon atoms. The haloalkyl radical may include such groups as chloroalkyl, fluoroalkyl, chlorofluoroalkyl, perfluoroalkyl, perchloroalkyl, perfluoroaryl, etc. I

Examples of suitable halo ketones or halo aldehydes include but are not limited to hexafluoroacetone, trifluoroacetaldehyde 1,1,1-trifluoroacetone, chloral, chloropentafluoroacetone, trifluoroacetophenone, pentafluorobenzaldehyde, etc. The compounds of the present invention are prepared by reaction essentially stoichiometric amounts of an ethylenimine (aziridine) or an N(w-aminoalkyl) aziridine with a suitable halo ketone or halo aldehyde.

The reaction can be carried out at temperatures ranging from about 70 C. to about 25 0., preferably from about -25 C. to about 0 C. Generally, the reaction is not carried out at temperatures above about 0 C. Atmospheric pressures are suitable; however, pressurized reaction vessels could also be employed. In general, the reaction appears to be instantaneous. Product precipitation usually occurs immediately after combination of equimolar amounts of aziridine and halocarbonyl compounds. Generally, the reaction mass is stirred, so as to insure complete reaction, preferably for a period of about 15 to about 30 minutes. No catalyst isnecessary and, in general, a'catalyst is not desirable.

The reaction is conducted in the presence of a liquid diluent or solvent. Suitable liquid diluents or solvents are inert. Non-limiting examples of such diluents or solvents include ether, acetone, halohydrocarbons, etc. A preferred diluent is diethyl ether. In general, about 1 to about 2 liters of diluent or solvent is employed per mole of reactant.

The reaction can be carried out in any suitable reactor in either a batch or continuous process. Preferably, a nitrogen blanket is employed so as to keep a dry inert atmosphere. The process is carried out by mixing the reactants in a suitable vessel maintained at temperatures within the ranges mentioned above. The reaction appears to take place spontaneously and the aminohydrin readily separates from solution. The resulting product is a solid material which can be separated from the reaction mass, for example, by filtration. If desired, the purity of the product may be increased by washing and/ or recrystallization. The resulting solid product is readily characterized by infrared and NMR spectroscopy and elemental analysis.

The present invention is further illustrated but not limited by the following examples.

EXAMPLE 1 2, 2,2-trichloro- 1- n-aziridyl) ethanol To 0.25 mole of chloral dissolved in 200 ml. of dry ether in a nitrogen purged four-necked flask fittedwith stirrer, thermometer, addition funnel and Dewar condenser was slowly added 0.25 mole of ethylenimine in 200 m1. of anhydrous ether. The mixture was kept at 0 C. and continually flushed with dry nitrogen. After complete ethylenimine addition, the aminohydrin separated from solution. The filtered product, obtained in 88% 3 yield, was recrystallized from acetone and its M.P. range V was 88489.

Analysis.Calculated for C H NOCl- C, 25.20; N, 7.35; Cl, 55.85. Found: C, 25.45; N, 7.35; C1, 55.90.

EXAMPLE 2 2,2,2-trifluoro-1-(n-aziridyl) ethanol In accordance with the procedure described in Example 1, a half mole of ethylenimine was added dropwise to a half mole of trifluoroacetaldehyde hydrate dissolved in 1 liter of ether. The reaction mixture was maintained at C. during the addition. The aminohydrin separated from solution after the ethylenimine addition Was completed. The recrystallized product (from acetone), M.P. 99-100 C., was obtained in 54% yield.

Analysis-Calculated for C H NOF C, 34.04; N, 9.92; F, 40.39. Found: C, 34.22; N, 9.83; F, 39.90.

EXAMPLE 3 1, 1, 1,3,3 ,3 -heXafiuoro-2- (N-aziridyl) -2-propanol To an ether solution of 0.5 mole hexafluoroacetone in a four-necked flask equipped with stirrer, thermometer, Dewar condenser and addition funnel was slowly added 0.5 mole of ethylenimine in ether solution. The reaction mixture was kept at 40 to 60 C. during the course of ethylenimine addition; after complete addition, a white copious solid separated from solution. The mixture was allowed to warm to room temperature and the solid product was filtered off. The aminohydrin was recrystallized from ether acetone and its M.P. range was 148150.

Analysis.-Calculated for C H NOF C, 28.76; N, 6.69; F, 54.55. Found: C, 29.04; N, 6.54; F, 54.50.

EXAMPLE 4 1,1, l,3,3,3-hexafluoro-2 [3 (N-aziridyl) -propylarnino] 2-propano1 A half mole of hexafluoroacetone was condensed into a reaction flask containing 0.5 mole of N(3-aminopropyl) aziridine in a liter of anhydrous ether at 40 to 60 C. After the halo ketone addition was complete, copious white solid precipitated from solution. Recrystallization from ether afforded a 90% aminohydrin having an M.P. range of 85-87 C. The NMR spectrum of the adduct in deuteroacetone showed the expected A B multiplet (ring protons) at 8.28 and 8.831.

Analysis-Calculated for C H N OF C, 36.10; N, 10.52; F, 42.82. Found: C, 36.88; N, 10.42; F, 42.90.

EXAMPLE 5 1,1,1,3,3,3 -hexafluoro-2 (N-aziridyl) ethylamino-2- propanol The addition of 1 mole of hexafluoroacetone to l mole of N(2-aminoethyl)aziridine in 1 liter of dry ether at C. gave a quantitative yield of aminohydrin having an M.P. range of 91-93 C. The proton spectrum in methanol-d showed diagnostic A B multiplets (ring hydrogens) at 8.17 and 8.647 in the expected intensity ratio.

Analysis-Calculated for C H ON F F, 45.21. Found: F, 45.20.

EXAMPLE 6 Compounds for this invention were tested for pesticidal activity. The compounds tested include those specifically listed below as well as other compounds falling under the general category of pesticidal aminohydrins as outlined above. e

Nematocidal activity of the aminohydrins against Panagrellus, an active saprozoic nematode, was evaluated as follows. In a test tube containing a nematode population of 50-70 per tube were placed 10 ml. of a chemical at the dosage to be tested. The test tube was stoppered and the percent mortality recorded at varying time intervals. The percent mortality at a dosage level of 50 p.p.m. is shown in Table I.

TABLE I.NEMATOCIDAL ACTIVITY The herbicidal action of the compounds of this invention was determined by a seed germination technique on a variety of crops carried out as follows: The compounds at a dosage level of 2,500 p.p.m. are pipetted in 5 cc. quantities onto filter paper contained within plastic petri dishes. Seeds of the selected crops are then placed on the treated disks and observed for germination over a certain period of time. The number of seeds germinating and the extent of root and cotyledon damage is an index of herbicidal potential of the aminohydrins. The herbicidal activity of the compounds of this invention are shown in Table II.

TABLE II.PRE-EMERGENCE HERBICIDAL ACTIVITY Wheat Cucumber Flax Tomato Radish Aziridine Percent germ Pr Percent germ Pr Percent germ Pr Percent germ Pr Percent germ Pr 0 F I N l-O H 0 10 96 8 0 10 78 5 4 9 C 01; DN 6 O H 0 10 U 10 U 10 0 10 0 10 CFQ EN 3 O H 0 10 100 8 0 1O 0 10 34 9 Percent gunk-percentage of seeds germinating. lr-phytotoxlcity rating wherein 0 equals normal growth and 10 indicates no growth.

EXAMPLE 8 In order to evaluate the pre-emergence activity of the aminohydrins of the present invention, a flat seeded with six representative crops is sprayed with a formulation containing the compound at a rate equivalent to pounds per acre and diethyl ether as solvent. The flats are then held in the greenhouse and the response rated after 12-16 days.

In evaluating the post-emergence activity of the aminohydrins the flats are seeded as described above and held until the first true leaves have appeared on all plants. Then they are sprayed in the same fashion as above. The plant responses are rated 12-16 days after treatment.

Table III shows both the preand post-emergence activity of the aminohydrins.

derivatives, sulfonated aromatic and mixed alkyl-aryl sul fonated derivatives, esters of fatty acids such as ricinoleic acid, the esters of sorbitol, salts of the petroleum sulfonic acids, the ethylene oxide condensation products of alkylated phenol, alcohols, or amines, or blends thereof, etc.

In addition to their primary utility as pesticides, compounds of the present invention may have other utilities such as reactive intermediates for the preparation of other pesticides, pharmaceuticals, or for the preparation of paper treatment chemicals and the like.

It is to be understood that this invention is not limited to the specific examples which have been oifered merely as illustrations, since other compounds can be prepared and other modifications made without departing from the 15 spirit of the invention.

TABLE III.POST AND PRE-EMERGENCE HERBICIDAL ACTIVITY Millet Rye Sorghum Aster Buckwheat Turnip Compound Post Pre Post Pre Post Pre Post Pre Post Pre Post Pre 0 F H l N(CH2)aN-(|3OH 4 5 4 5 3 5 2 3 2 4 2 1 C Fa C F: H N(CH2)2N-COH 4 5 4 5 4 5 5 5 4 5 3 3 1No injury, 2Slow injury, 3Moderate injury,

As is apparent from the above, the compounds of the present invention have utility as pesticides. As employed herein, the term pesticide is intended to mean any chemi cal compound useful in pest control. Thus, the term pesticide includes compounds which function either as an insecticide, a fungicide, a herbicide, a rodenticide, a nematocide or the like. As is apparent from the above examples, a particular compound of the present invention may exhibit one or more different pesticidal activities. The compounds have particular utility as herbicides.

The pesticidally active compounds of this invention can be employed singly or as a mixture with other pesticidal agents. Pesticidal compositions or formulations containing the compounds of this invention can be prepared by methods well known to those skilled in the art. Thus, for example, depending upon the physical characteristics of the particular aminohydrin, it can be applied as an undiluted spray or may be reduced to an impalpable powder and applied as an undiluted dust, or mixed with a solid carrier such as clay, talc, limestone, bentonite, diatomaceous earth, fullers earth, silica gel, pyrophillite, gypsum and similar materials in a finely divided or comminuted form well known in the art. The compounds of this invention may be applied as a spray in a liquid carrier, as a solution in a solvent, or as a suspension in a nonsolvent. Suitable solvents include petroleum fractions such as kerosene, diesel oil, etc. aromatic hydrocarbons such as cumene, benzene, toluene, xylene, etc., alcohols such as isobutanol, methanol, ethanol, isopropanol, etc.; ketones such as acetone or methylethylketone; esters such as ethyl acetate, methyl formate, n-butyl acetates, isobu'tyl acetate, ethyl propionate, etc. halogenated hydrocarbons such as perchloroethylene, methylene chloride, carbon tetrachloride, chloroform, ethylene dichloride, etc.; paraffinic hydrocarbons such as pentane, isopentane, cyclopentane, isohexane, n-hexane, cyclohexane, n-heptane, etc. When applied as a spray in water, it may be desirable to incorporate wetting agents and/or dispersing agents compatible with the active aminohydrin ingredient.

Among the various wetting and dispersing agents of utility in this invention are the alkali metal salts of sulfates of long, straight or branched chain alcohols such as dodecanol up to octadecanol, sulfonated amide and ester 4Severe injury, 5-Ki1led.

What is claimed is:

1. A herbicidal composition comprising an eliective amount of an active ingredient consisting essentially of a compound of the formula R Y-(J-OH where Y is selected from the group consisting of and groups; n is an integer of from 2 to 4 inclusive; residue R is lower haloalkyl; and R is an organo radical selected from the group consisting of hydrogen, lower alkyl, lower haloalkyl, phenyl and halo-subs. phenyl; in combination with an inert carrier.

2. A composition as defined by claim 1 wherein said inert carrier is a solvent.

3. A composition as defined by claim 1 in the form of a dust.

4. A composition as defined by claim 1 in the form of an aqueous emulsion.

5. A method of destroying undesired vegetation which comprises contacting said vegetation with an effective amount of a compound having the formula:

R Y-(iI-OH where Y is selected from the group consisting of and groups; n is an integer of from 2 to 4 inclusive; residue R is lower haloalkyl; and R is an organo radical selected from the group consisting of hydrogen, lower alkyl, lower haloalkyl, phenyl and halo-subs. phenyl.

where Y is selected from the group consisting of and groups; n is an integer of from 2 to 4 inclusive; residue R is lower haloalkyl; and R is an organo radical selected from the group consisting of hydrogen, lower alkyl, lower haloalkyl, phenyl and halo-subs. phenyl and an inert carrier.

7. A method as defined by claim 6 wherein said carrier is water.

8. A herbicidal composition comprising an effective amount of an active ingredient consisting essentially of a compound of the formula CF; DN(CH2)nHNJ:/'OH

F 3 wherein n is an integral number of from 2 to 4 inclusive; in combination with an inert carrier.

9. A composition as defined by claim 8 wherein said compound is 8 10. A method as defined by claim 6 wherein said compound is a compound of the formula F I N( CHzhHN-(J-OH 6 F3 wherein n is an integral number of from 2 to 4 inclusive.

11. A method as defined by claim 6 wherein said compound is I N(CIIz)uHN(|JOH References Cited UNITED STATES PATENTS 2,809,912 10/1957, Birum 16733 3,197,465 7/1965 Woods et al. 167-33 3,208,905 9/1965 Ristich et a1. 167 33 3,243,429 3/1966 Ham 26G239 3,297,682 1/1967 Kuhn 260239 3,314,848 4/1967 Ratz et a1. 16713 3,324,112 6/1967 Ottmann et a1. 260-239 3,335,132 8/1967 Kuhn 71-88 3,401,164 9/1968 Brois 7188 FOREIGN PATENTS 1,060,439 3/1967 Great Britain.

30 OTHER REFERENCES Kostyanovskii, Doklady Akad. Nauk SSSR, vol. 139, pp. 877-879 (1961).

LEWIS GOTTS, Primary Examiner 5 G. HOLLRAH, Assistant Examiner US. Cl. X.R. 260239; 424-244 

